Process of obtaining beryllium compounds from beryllium-bearing minerals



The treatment of such minerals or ores has important however, that an excess -of a Patented Aug. 25, 1931 UNITED STATES PA E T OFFICE *mw'r rrscnmor nEBLm-rnmnanao, 0121mm, nssrorron, BY mrsnn Assmm.

, HEN'I'S, TO METAL & THEBHIT CORPORATION, OF NEW YORK, N. Y A CORPORATION OF NEW JERSEY PROCESS. Oil? OBTAINING- BEBYLLIUI COIPOUNDS FROM BEBYLLIUM-BEABING R0 Drawing; Application med December 18, 1928, Serial No. 825,927, and in Germany December 15, 1927.

My invention relates to the treatment of ble is made, is practically not attacked at minerals containing beryllium, for the purall. process enables me to obtain from pose of obtaining therefrom be llium comthe minerals up to about 90% of the theopounds, and particularly bery lium salts. retical content of beryllium. Itis higlliily a 1 offered considerable practical difiiculties carbonate should be employed. which are due mostly 'to the fact that only a The coherent mass resulting from the sinrelatively smallpercentage of beryllium is )term action is then comminuted, which can: contained in such minerals. For instance, be e ected without any practical difliculty,

-1o beryl (a silicate of beryllium and alumin and is then subjected to further treatment.

ium) which is a mineral of rather frequent {in advantageous method consists in treatoccurrence,'contains a verylarge amountof mg the mass, after it has been comminuted, gangue consisting chiefly of, silica, alumina, with the solution of a hydrogen halide, for and iron, the gangue amounting up to 90% Instance hydrochlorlc acid, w ereb a thick 1 of the mineral. Heretofore, so far as I paste is obtained. The latter is a ded to a k w, th r wa n ti f t vprocess f r solution of sodium bicarbonate. I am thus the industrial treatment of such berylliumenabled to ac mphsh a practlcally complete b i g mi ral Th 11 d t s separation of the beryllium salt from the rd t hi h th i l ft r entire gangue portion in a single operation,

2Q minution was treated with'an acid, produced since the sodium bicarbonate SOllltlOl'l will but a relatively small yieldof ber'llium,

f whereas the so-called dry processes, w ich as a rule involve melting the beryllium-bearing mineral together with oxides or carbonatesof alkali metals, were objectionable on ac- ,count of the high temperatures employed and of the resulting strain and wear of the material of which the crucible was made. Another objection to the dry process is found so in the difliculty of comminuting the material under treatment. j

My present invention relates to a process which I am enabled to obtain a good yield .ofberyllium compounds from berylliumbearing minerals, while avoidin the drawbacks of the processes emlployed 'itherto;

For this purpose -I rst comminute a beryllium-bearing'mineral and then heat it in the presence of an excess of alkali metal 4 carbonatev to tem ratures which are relatively high, but still below the melting point of the mixture. The result of this heating, which is preferably continued for several hours, is a sintered mass,especial care being taken to avoid any melting of the mixture.

- The ulverulent mixture contracts during sintering, and, in contradistinction to what occurs in the previously employed dry processes, can be removed readily from the crucible. The material of which the crucidissolve only beryllium, whereas the other constituents remain undissolved. The separation of-the solution from the undissolved residue may be effected in any suitable manner, for instance by decanting.

I An important feature of this operation is the simultaneous separation of the beryllium salt from the silica and the other foreignmetal compounds. The berryllium salt obtained from the. alkali metal bicarbonate solution according to any well-known or approved process, may then be subjected to any suitable further treatment for the purose' of obtaining other beryllium salts thererom. 4

Occasionally it will be found that berylliumsalts obtained according to the process above set forth contain a slight proportion of iron, which ma come either from the original mineral or rom impurities of the chemical reagents employed, If it be desired to remove such traces of iron from the beryllium salts, I may take advantage of the hitherto unknown fa't that the addition of a small amountofammonium sulphide to a solution which contains a relativelylarge amount of beryllium and a relatively small amount of-iron, will first pre-' cipitate the iron in the form of sul hide and only subsequently precipitate the ryllium readil 'in the form of hydroxide. In such cases therefore, the be llium salt contaminated by iron is dissolve an l'to the solution I add a'small amount of ammonium sulphide, about as much as'corresponds to the amount of iron present. This will cause a practically quantitative perci itation of. iron in theform of sulphide, so t at subsequent separation of the liquid from the precipitate (say, by filtration) will yield beryllium salts practically free from iron, It is preferable to heat the solution after filtration to a relatively high temperature, or better still, to concentrate it by evaporation, in order'to drive off any remaining traces of ammonium sul hide. Y

give an example I may proceed as follows: Beryl mineral such as is found in nature, is powdered very finely and then mixed withsodium carbonate in the proportion of about one part (by weight) of beryl to two parts of sodium carbonate. The mixture is heated in a refractory crucible for about two or three hours to atemperature of approximately 700 0., care being taken to A avoid fusion of the mass. -.This heating transforms the powdered material into a sintered coherent mass which can be removed from the crucible. after its removal is comminuted in any suitable manner and by the addition of hydrochloric acid, it is converted into a paste which is added to a solution of sodium bicarbonate. For instance, if the raw material consisted of '10 kilograms of beryl, the thick pasteobtained by the addition of hydroof a 15 chloric acid maybe added to about 140 liters r cent. solution of sodium bicarbonate. t is desirable to heat this solution to about C. Suchtreatment will cause the aluminium compounds, the iron compounds, and silica to remain almost entirely undissolved, whereas beryllium is dissolved and may be separated from the residue readily, for instance by filtration. From this berylhum solution the particular salts which it is desired to produce, may be ob-- tained in any well-known or approved manner; for instance the addition of hydrofluoric acid will produce beryllium fluoride.

In the event that the beryllium salts should still contain iron, the latter may be removed in the following manner: If, for

instance, the process described above yields 10 kilograms of berylliumfluoride with an iron content of about .2 per cent.,' such fluoride is dissolved in a small quantity of water say about from 10 to 15 liters. To this beryllium fluoride solution I thenadd about 400 cubic centimeters of a 10per cent, solution of ammonium sulphide under continual stirring, at ordinaryroom temperature. This treatment will produce a precipitate consisting exclusively ofiron sulphide. The solution is their preferably allowed to stand Such mass.

for several hours, in order to "ve the iron sulphide an opportunity to col ect or settle at the bottom of the rece tacle. The supernatant, practically ironree solution can be separated from the precipitate in any su1ta-' ble manner, for instance by decantation.

The solution is then concentrated by evaporation, which causes any remaining traces of ammonium sulphide to become volatilized,

major constituent of the molten mass in tended for the production of compact metallic beryllium by electrolysis of a molten'bath. While I have referred to the removal' of obtained in the specific manner described above, I desire it to be understood that the above described steps for removing iron Zsmallamounts of iron from beryllium-salts from beryllium salts may be used 1n'connection with beryllium salts obtained by any other process.

I claim:

compounds from beryllium-bearing minerals, which comprisescomminuting a berylliumbearing mineral, adding thereto pulverulent alkali metal carbonate used in excess, heat- 1. The process of obtaining beryllium ing both of said substances together to a relatively high temperature,- but below their melting points, fora length of time suflicient to convert said substances into a sintered mass, commmuting sald mass, and subjecting it to further treatment for the pro duction of beryllium compounds.

2. The process of obtaining beryllium compounds from beryllium-bearing minerals, .which comprises mixing a finely com minuted beryllium mineral with alkali metal carbonate used in excess, heating the mix- .t lre to a relatively high temperature, but

below the melting point of such mixture, for a length of time suflicient to convert said mixture into a sintered mass, commmuting such mass, adding thereto a solution of a hydrogen halide to form a paste, adding such aste to a solution of an alkali metal car- Eonate, and separating the resultin solution of beryllium compounds fromt e undissolved constituents.

3. The process of obtaining beryllium compounds from beryllium-bearing minerals, which comprises sintering a pulverulent beryllium-bearing mineral together with sodium carbonate used in excess, comminutin the sintered mass, adding hydrochloric aci thereto'to form a paste, mixing such paste with a solution of sodium bicarbonate, heat-- ingthe mixture to about'50 centigrade, and separating the resulting solution of beryllium compounds from the undissolved residue.

4. The process of obtaining beryllium compounds from beryllium-bearin minerals, WhlCh comprlses smterm a pn verulent beryllium-bean m neral a mixed wlth sodium carbonate in excess, treating the sintered mass with h drochloric acid to form a Easte, adding sai paste to a sodium bicaronate solutlon, separating the clear solution from the recipitate, adding-hydrofluoric acid to t e solutionto form beryllium fluoride, treating beryllium fluoride in solution with about the uantity of ammonium sulphide to precipitate any iron present, removing the (freclpitate and separating the so purifie beryllium fluoride from the solution,

In testimony whereof I aifix my signature.

HELLMUT FISCHER. 

